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971.
Choi EM Kwak SJ Kim YM Ha KS Kim JI Lee SW Han JA 《Experimental & molecular medicine》2005,37(3):199-203
Cyclooxygenase-2 (COX-2) has been reported to be associated with tumor development and progression as well as to protect cells from apoptosis induced by various cellular stresses. Through a tetracycline-regulated COX-2 overexpression system, we found that COX-2 inhibits detachment-induced apoptosis (anoikis) in a human bladder cancer cell line, EJ. We also found that the inhibition of anoikis by COX-2 results from activation of the PI-3K/Akt pathway as evidenced by suppression of the COX-2 effect on anoikis by a PI-3K inhibitor, LY294002. Furthermore, COX-2 enhanced Mcl-1 expression in the anoikis process, implying that Mcl-1 also may be involved in mediating the survival function of COX-2. Together, these results suggest that COX-2 inhibits anoikis by activation of the PI-3K/Akt pathway and probably by enhancement of Mcl-1 expression in human bladder cancer cells. This anti- anoikis effect of COX-2 may be a part of mechanisms to promote tumor development and progression. 相似文献
972.
A mild protocol for the palladium-catalyzed Buchwald-Hartwig amidation of icosahedral carboranes is described. Employing 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl (1) as a ligand and K(3)PO(4) as a base, benzamide, trifluoroacetamide, acetamide, and formamide were coupled to a series of mono- and di-iodo carboranes furnishing the respective carborane derivatives in good to excellent yields. Subsequent base-mediated saponification of the trifluoroacetamide derivatives was shown to provide the free aminocarboranes. The structures of N-(1,7-dicarba-closo-dodecaboran-9-yl)benzamide (8a), N-(1,7-dicarba-closo-dodecaboran-9-yl)trifluoroacetamide (8b), N-(1,12-dicarba-closo-dodecaboran-2-yl)benzamide (10a), N-(1,2-dicarba-closo-dodecaboran-9-yl)benzamide (12a), N-(1,2-dicarba-closo-dodecaboran-9-yl)acetamide (12c), N-(1,2-dicarba-closo-dodecaboran-9-yl)formamide (12d), N-(1,2-dicarba-closo-dodecaboran-3-yl)benzamide (13a), N,N'-(1,7-dicarba-closo-dodecaboran-9,10-diyl)dibenzamide (15a), and N,N'-(1,7-dicarba-closo-dodecaboran-9,10-diyl)bis(trifluoroacetamide) (15b) have been established through X-ray single-crystal diffraction studies. 相似文献
973.
Dr. Pravin Kumar Ankush Jagtap Dr. Sam Asami Claudia Sippel Prof. Dr. Ville R. I. Kaila Prof. Dr. Felix Hausch Prof. Dr. Michael Sattler 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9529-9533
The recently discovered SAFit class of inhibitors against the Hsp90 co‐chaperone FKBP51 show greater than 10 000‐fold selectivity over its closely related paralogue FKBP52. However, the mechanism underlying this selectivity remained unknown. By combining NMR spectroscopy, biophysical and computational methods with mutational analysis, we show that the SAFit molecules bind to a transient pocket in FKBP51. This represents a weakly populated conformation resembling the inhibitor‐bound state of FKBP51, suggesting conformational selection rather than induced fit as the major binding mechanism. The inhibitor‐bound conformation of FKBP51 is stabilized by an allosteric network of residues located away from the inhibitor‐binding site. These residues stabilize the Phe67 side chain in a dynamic outward conformation and are distinct in FKBP52, thus rationalizing the basis for the selectivity of SAFit inhibitors. Our results represent a paradigm for the selective inhibition of transient binding pockets. 相似文献
974.
Timothy R. Wilson Malavikha Rajivmoorthy Jordan Goss Sam Riddle Prof. Mark E. Eberhart 《Chemphyschem》2019,20(24):3289-3305
Our curiosity-driven desire to “see” chemical bonds dates back at least one-hundred years, perhaps to antiquity. Sweeping improvements in the accuracy of measured and predicted electron charge densities, alongside our largely bondcentric understanding of molecules and materials, heighten this desire with means and significance. Here we present a method for analyzing chemical bonds and their energy distributions in a two-dimensional projected space called the condensed charge density. Bond “silhouettes” in the condensed charge density can be reverse-projected to reveal precise three-dimensional bonding regions we call bond bundles. We show that delocalized metallic bonds and organic covalent bonds alike can be objectively analyzed, the formation of bonds observed, and that the crystallographic structure of simple metals can be rationalized in terms of bond bundle structure. Our method also reproduces the expected results of organic chemistry, enabling the recontextualization of existing bond models from a charge density perspective. 相似文献
975.
William F. Manders Jon M. Bellama Rolf B. Johannesen Edwin J. Parks Frederick E. Brinckman 《Journal of polymer science. Part A, Polymer chemistry》1987,25(12):3469-3477
The 1:1 and 2:1 formulations of the free radical initiated copolymers of methyl methacrylate (MMA) and tri-n-butyltin methacrylate (TBTM), and the homopolymer, poly(TBTM), are characterized by 13C- and 119C-NMR structural analyses were performed on the tributyltin-free hydrolyzate, a copolymer of MMA and methacrcylic acid (MAA). Configurational sequencing at the triad level is performed using the α-methyl region of the 13C-NMR spectrum. The probability of isotactic (meso) dyad placement at 80°C in the homopolymer (0.19) is determined to be significantly less than the probabilities observed for the copolymers (0.23–0.24). Random compositional sequencing is established for the copolymers through a comparison of the carbonyl regions of the 13C-NMR spectra of the hydrolyzates with the carbonyl regions in published spectra of structurally characterized copolymers of MMA and MAA. The 119Sn chemical shift and the tin-carbon J coupling for the polymers are dependent on the solvent employed. This dependence is attributed to electron donor or acceptor interactions between the solvent and the strong Sn? O dipole. The tin-containing copolymers exhibit multiple 119Sn resonances, which appear related to compositional sequencing. 相似文献
976.
Frederick Bloom 《Journal of Mathematical Analysis and Applications》1977,58(2):293-297
Conditions are given under which members of a class of uniformly bounded solutions to the Cauchy problem associated with equations of the form Mutt ? Nu = F, in Hilbert space, depend continuously on perturbations of the initial geometry; our results generalize a similar theorem of Knops and Payne for classical solutions to initial-boundary value problems in linear elastodynamics. 相似文献
977.
Aliev AE Mann SE Rahman AS McMillan PF Corà F Iuga D Hughes CE Harris KD 《The journal of physical chemistry. A》2011,115(44):12201-12211
High-resolution solid-state (2)H MAS NMR studies of the α and γ polymorphs of fully deuterated glycine (glycine-d(5)) are reported. Analysis of spinning sideband patterns is used to determine the (2)H quadrupole interaction parameters, and is shown to yield good agreement with the corresponding parameters determined from single-crystal (2)H NMR measurements (the maximum deviation in quadrupole coupling constants determined from these two approaches is only 1%). From analysis of simulated (2)H MAS NMR sideband patterns as a function of reorientational jump frequency (κ) for the -N(+)D(3) group in glycine-d(5), the experimentally observed differences in the (2)H MAS NMR spectrum for the -N(+)D(3) deutrons in the α and γ polymorphs is attributed to differences in the rate of reorientation of the -N(+)D(3) group. These simulations show severe broadening of the (2)H MAS NMR signal in the intermediate motion regime, suggesting that deuterons undergoing reorientational motions at rates in the range κ ≈ 10(4)-10(6) s(-1) are likely to be undetectable in (2)H MAS NMR measurements for materials with natural isotopic abundances. The (1)H NMR chemical shifts for the α and γ polymorphs of glycine have been determined from the (2)H MAS NMR results, taking into account the known second-order shift. Further quantum mechanical calculations of (2)H quadrupole interaction parameters and (1)H chemical shifts reveal the structural dependence of these parameters in the two polymorphs and suggest that the existence of two short intermolecular C-H···O contacts for one of the H atoms of the >CH(2) group in the α polymorph have a significant influence on the (2)H quadrupole coupling and (1)H chemical shift for this site. 相似文献
978.
Douglas E. Weiss Denise A. Cleghorn Sam V. Nablo 《Radiation Physics and Chemistry》2002,63(3-6):581-586
The application of low-energy electrons for the disinfection of containers of complex geometries has been limited due to their inability to efficiently penetrate the rigid walls. Most three-dimensional applications have been evaluated using higher energy processors with bulk or through-the-wall treatment. This work has been directed to the validation of electron disinfection of interior surfaces by injecting electrons through the open-mouth of the container. Both direct thin-film dosimetric mapping of the interior and exterior dose distributions for in-line treatment have been conducted and compared with the results of Monte Carlo modeling utilizing 106 or more source electron histories. Sterilizer characterization and model assumptions are described and the advantages of the modeling technique for process parameter optimization discussed. 相似文献
979.
Ray H. Liu I. A. Low Frederick P. Smith Edwin G. Piotrowski An-fei Hsu 《Journal of mass spectrometry : JMS》1985,20(8):511-514
The ion-molecular reaction behavior of ten morphine alkaloids with several commonly used reagent gases are studied under chemical ionization mass spectrometry conditions. These studies emphasize the correlation of the structural characteristics of the 10 alkaloids with the following four mass spectrometric parameters: (i) mass shifts of the protonated ion as a result of replacing ammonia with deuterated ammonia as the reagent gas, (ii) relative tendencies of the adduct ion and the protonated ion to lose molecules of water, (iii) relative intensity ratio of the adduct ion and the protonated ion and (iv) tendency of a compound to undergo a reduction reaction. 相似文献
980.